P
US7524358B2ExpiredUtilityPatentIndex 91

Production of high purity and ultra-high purity gas

Assignee: PRAXAIR TECHNOLOGY INCPriority: May 31, 2002Filed: May 30, 2003Granted: Apr 28, 2009
Est. expiryMay 31, 2022(expired)· nominal 20-yr term from priority
Inventors:SAXENA HIMANSHUACKLEY MARK WILLIAMBILLINGHAM JOHN FREDRICBARRETT PHILIP ALEXANDER
B01D 2256/16B01D 2257/502F25J 3/04169F25J 3/04163B01J 2219/00006F25J 2215/44B01D 2259/4009B01D 2259/4146Y02C20/10B01D 53/261Y02C20/40B01J 2208/00274B01D 2257/108B01D 2259/402B01D 2257/504B01D 53/0462B01D 2253/25B01D 53/047B01D 53/864B01D 2253/30F25J 2205/82B01D 2257/80B01D 2257/404B01D 53/0431B01D 2253/1085B01J 2219/00038B01D 2253/106B01D 2259/416B01D 2253/108B01D 2257/50B01D 53/0454B01D 53/04B01D 53/02B01D 2253/104B01D 2256/245B01D 2256/10B01J 8/025B01D 2256/18B01D 2257/702
91
PatentIndex Score
28
Cited by
42
References
58
Claims

Abstract

Trace amounts of carbon monoxide and optionally hydrogen are removed from gaseous feed streams by passing the feed stream through a carbon monoxide adsorbent ( 33 ) prior to passing it through a supported metal catalyst ( 34 ). The invention saves significant capital and operational costs over existing processes.

Claims

exact text as granted — not AI-modified
1. An adsorption apparatus for the removal of CO from a feed stream containing CO in an amount of less than 50 ppm, said apparatus comprising at least one adsorption vessel containing a CO adsorbent layer, the CO adsorbent having a ΔCO working capacity greater than or equal to 0.01 mmol/g, and a source which supplies said feed stream, wherein
 a) when said feed stream further contains at least one gas selected from the group consisting of nitrogen, He, Ne, Ar, Xe, Kr, CH 4  and mixtures thereof, said adsorbent is ion exchanged with a Group IB element; or 
 b) when said feed stream further contains at least one gas selected from the group consisting of oxygen and air and mixtures thereof, said adsorbent is a zeolite having a SiO 2 /Al 2 O 3  ratio of <20, and is ion-exchanged with a Ag +  or Au + . 
 
     
     
       2. The apparatus of  claim 1 , wherein said apparatus contains two or more of said adsorption vessels. 
     
     
       3. The apparatus of  claim 1 , wherein said adsorption vessel is selected from the group consisting of vertical flow vessels, horizontal flow vessels, lateral flow vessels or radial flow vessels. 
     
     
       4. The adsorption apparatus of  claim 1 , wherein said apparatus further contains an adsorbent selective for the adsorption of water, and wherein the water selective adsorbent layer is upstream of said CO adsorbent layer. 
     
     
       5. The adsorption apparatus of  claim 1 , wherein said apparatus further contains a catalyst layer for the catalytic oxidation of H 2  to H 2 O, and wherein said catalyst layer is downstream of said CO adsorbent layer. 
     
     
       6. The adsorption apparatus of  claim 5 , wherein said apparatus further contains an auxiliary adsorbent for the removal of water, and wherein said auxiliary adsorbent is downstream of said catalyst layer. 
     
     
       7. The apparatus of  claim 1 , wherein said ΔCO working capacity is greater than or equal to 0.03 mmol/g. 
     
     
       8. The apparatus of  claim 4 , wherein the water selective adsorbent is one or more of alumina or NaX zeolite. 
     
     
       9. The apparatus of  claim 5 , wherein the H 2  catalyst is a supported metal catalyst. 
     
     
       10. The apparatus of  claim 9 , wherein said supported metal catalyst comprises one or more of the metals Os, Ir, Pt, Ru, Rh, Pd, Fe, Co, Ni, Cu, Ag, Au, Zn, Sn, Mn, Cr, Pb, Ce and is supported on a substrate selected from the group consisting of alumina, silica, natural or synthetic zeolites, titanium dioxide, magnesium oxide and calcium oxide. 
     
     
       11. The apparatus of  claim 1 , wherein said apparatus further contains:
 a) at least one adsorbent layer upstream of said CO adsorbent for the adsorption of one or more of H 2 O and CO 2 , 
 b) a catalyst layer for the catalytic conversion of H 2  to H 2 O that is downstream of said CO adsorbent layer; and 
 c) one or more additional adsorbents for the adsorption of one or more of H 2 O, CO 2 , N 2 O and hydrocarbons, wherein said additional adsorbents are downstream of said catalyst layer. 
 
     
     
       12. The apparatus of  claim 11 , wherein said one or more additional adsorbents are selected from the group consisting of alumina, silica gel, clinoptilolite, zeolites, composites thereof and mixtures thereof. 
     
     
       13. The apparatus of  claim 1 , wherein the CO adsorbent has a ΔCO/ΔN 2  separation factor of greater than or equal to 1×10 −3 . 
     
     
       14. The apparatus of  claim 1 , wherein when said feed stream further contains at least one gas selected from the group consisting of nitrogen, He, Ne, Ar, Xe, Kr, H 2 , CH 4  and mixtures thereof, said CO adsorbent is selected from the group consisting of AgX zeolite, Ag-Mordenite, Cu-clinoptilolite, AgA zeolite and AgY zeolite. 
     
     
       15. The apparatus of  claim 1 , wherein when said feed stream further contains at least one gas selected from the group consisting of oxygen and air and mixtures thereof, said CO adsorbent is selected from the group consisting of AgX zeolite, Ag-Mordenite, AgA zeolite and AgY zeolite. 
     
     
       16. The apparatus of  claim 1 , wherein said CO adsorbent is AgX zeolite. 
     
     
       17. The apparatus of  claims 1 , wherein when said feed gas further contains air, said apparatus is an air prepurifier. 
     
     
       18. The apparatus of  claim 1 , wherein said CO adsorbent is AgX having 100% of its cations associated with Ag. 
     
     
       19. A process for the removal of CO from a feed stream containing CO in an amount of less than 50 ppm, said process comprising contacting said feed stream with a CO adsorbent having a ΔCO working capacity greater than or equal to 0.01 mmol/g to produce a CO depleted gas stream; and wherein
 a) when said feed stream further contains at least one gas selected from the group consisting of nitrogen, He, Ne, Ar, Xe, Kr, H 2 , CH 4  and mixtures thereof, said adsorbent is a zeolite exchanged with a Group IB element; or 
 b) when said feed stream further contains at least one gas selected from the group consisting of oxygen and air and mixtures thereof, said adsorbent is a zeolite having a SiO 2 /Al 2 O 3  ratio of <20, and is ion-exchanged with a Ag +  or Au + . 
 
     
     
       20. The process of  claim 19 , further comprising recovering said CO depleted gas stream, wherein CO is present in said CO depleted gas stream at a concentration of less than 100 ppb. 
     
     
       21. The process of  claim 19 , further comprising recovering said CO depleted gas stream, wherein CO is present in said CO depleted gas stream at a concentration of less than 5 ppb. 
     
     
       22. The process of  claim 19 , wherein said CO concentration in said feed stream is less than 1 ppm CO. 
     
     
       23. The process of  claim 19 , wherein said CO concentration in said feed stream is less than 0.5 ppm CO. 
     
     
       24. The process of  claim 19 , wherein said feed gas further comprises water (H 2 O), and said process further comprises contacting said feed stream with a water selective adsorbent that is located upstream of said CO adsorbent. 
     
     
       25. The process of  claim 19 , wherein said feed gas further comprises hydrogen, and said process further comprises contacting said CO depleted feed stream with a catalyst layer for the catalytic oxidation of H 2  to H 2 O to produce a H 2  depleted and H 2 O enriched gas, and wherein said catalyst layer is located downstream of said CO adsorbent layer. 
     
     
       26. The process of  claim 25 , wherein said process further comprises the step of contacting said H 2 O enriched gas with an adsorbent for the removal of water, and wherein the H 2 O adsorbent layer is located downstream of said catalyst layer to produce a gas that is depleted in CO, H 2  and H 2 O. 
     
     
       27. The process of  claim 19 , wherein said ΔCO working capacity is greater than or equal to 0.03 mmol/g. 
     
     
       28. The process of  claim 19 , wherein the CO adsorbent has a ΔCO/ΔN 2  separation factor that is greater than or equal to 1×10 −3 . 
     
     
       29. The process of  claim 19 , wherein the CO adsorbent has a ΔCO/ΔN 2  separation factor that is greater than or equal to 1×10 −2 . 
     
     
       30. The process of  claim 24 , wherein the water selective adsorbent is one or more of alumina or NaX. 
     
     
       31. The process of  claim 25 , wherein the catalyst is a supported metal catalyst. 
     
     
       32. The process of  claim 31 , wherein said supported metal catalyst is comprises one or more of the metals Os, Ir, Pt, Ru, Rh, Pd, Fe, Co, Ni, Cu, Ag, Au, Zn, Sn, Mn, Cr, Pb, Ce and is supported on a substrate selected from the group consisting of alumina, silica, natural or synthetic zeolites, titanium dioxide, magnesium oxide and calcium oxide. 
     
     
       33. The process of  claim 19 , wherein said process further comprises passing said feed gas over:
 a) at least one adsorbent layer upstream of said CO adsorbent for the adsorption of one or more of H 2 O and CO 2 , 
 b) a catalyst layer for the catalytic conversion of H 2  to H 2 O that is downstream of said CO adsorbent layer; and 
 c) one or more additional adsorbents for the adsorption of one or more of H 2 O, CO 2 , N 2 O and hydrocarbons, wherein said additional adsorbents are downstream of said catalyst layer. 
 
     
     
       34. The process of  claim 33 , wherein said one or more additional adsorbents are selected from the group consisting of alumina, silica gel, clinoptilolite, zeolites, composites thereof and mixtures thereof. 
     
     
       35. The process of  claim 19 , wherein said process is selected from the group consisting of pressure swing adsorption, temperature swing adsorption, or a combination thereof. 
     
     
       36. The process of  claim 19 , wherein said process takes place in an adsorber vessel selected from a vertical flow vessel, a horizontal flow vessel or a radial flow vessel. 
     
     
       37. The process of  claim 25 , wherein the hydrogen depleted gas contains less than 100 ppb hydrogen. 
     
     
       38. The process of  claim 25 , wherein the hydrogen depleted gas contains less than 5 ppb hydrogen. 
     
     
       39. The process of  claim 19 , wherein the adsorption step of said process is operated at a temperature of zero to fifty degrees Celsius. 
     
     
       40. The process of  claim 19 , wherein when said feed gas further contains at least one gas selected from the group consisting of nitrogen, He, Ne, Ar, Xe, Kr, H 2 , CH 4  and mixtures thereof said CO adsorbent is selected from the group consisting of AgX, Ag-Mor, Cu-clinoptilolite, AgA zeolite and AgY zeolite. 
     
     
       41. The process of  claim 19 , wherein when said feed gas further contains at least one gas selected from the group consisting of air and oxygen and mixtures thereof said CO adsorbent is selected from the group consisting of AgX, Ag-Mor, AgA zeolite and AgY zeolite. 
     
     
       42. The process of  claim 19 , wherein said CO adsorbent is AgX having greater than 50% of its cations associated with Ag. 
     
     
       43. The process of  claim 19 , wherein said CO adsorbent is AgX having 100% of its cations associated with Ag. 
     
     
       44. The process of  claim 19 , wherein said feed stream contains air, and wherein said CO depleted gas stream is passed to a cryogenic distillation column. 
     
     
       45. The process of  claim 19 , further comprising recovering said CO depleted gas stream, wherein CO is present in said CO depleted gas stream at a concentration of less than 1 ppb. 
     
     
       46. The process of  claim 19 , wherein the CO partial pressure in said feed stream is less than 0.1 mmHg. 
     
     
       47. The process of  claim 19 , wherein the CO partial pressure in said feed stream is less than 0.005 mmHg. 
     
     
       48. A process for the removal of CO from a feed stream containing CO in an amount of less than 50 ppm and hydrogen said process comprising contacting said feed stream with a CO adsorbent having a ΔCO working capacity greater than or equal to 0.01 mmol/g to produce a CO depleted gas stream; and wherein said adsorbent is a zeolite exchanged with a Group IB element. 
     
     
       49. An adsorption apparatus for the removal of CO from a feed stream containing CO in an amount of less than 50 ppm, and hydrogen, said apparatus comprising at least one adsorption vessel containing a CO adsorbent layer, the CO adsorbent having a ΔCO working capacity greater than or equal to 0.01 mmol/g; and wherein said adsorbent is a zeolite exchanged with a Group IB element, and a source which supplies said feed stream. 
     
     
       50. An air prepurification adsorption apparatus for the removal of CO from an air feed stream containing CO in an amount of less than 50 ppm, said apparatus comprising at least one adsorption vessel containing a CO adsorbent layer, the CO adsorbent having a ΔCO working capacity greater than or equal to 0.01 mmol/g, and a source which supplies said feed stream, and 
       wherein said adsorbent is a zeolite having a SiO 2 /Al 2 O 3  ratio of <20, and is ion-exchanged with a Ag +  or Au + . 
     
     
       51. The apparatus of  claim 50 , wherein said apparatus further comprises at least one adsorbent layer upstream of said CO adsorbent for the adsorption of one or more of H 2 O and CO 2 . 
     
     
       52. The apparatus of  claim 49  or  claim 50 , further comprising a catalyst layer for the catalytic conversion of H 2  to H 2 O that is downstream of said CO adsorbent layer; and one or more additional adsorbents for the adsorption of one or more of H 2 O, CO 2 , N 2 O and hydrocarbons, wherein said additional adsorbents are downstream of said catalyst layer. 
     
     
       53. The apparatus of  claim 49  or  claim 50 , wherein said CO adsorbent is AgX. 
     
     
       54. A process for the removal of CO from a feed stream containing CO in an amount of less than 50 ppm and air said process comprising contacting said feed stream in an adsorber vessel with a CO adsorbent having a ΔCO working capacity greater than or equal to 0.01 mmol/g to produce a CO depleted gas stream; and 
       wherein_said adsorbent is a zeolite having a SiO 2 /Al 2 O 3  ratio of <20, and is ion-exchanged with a Ag +  or Au + . 
     
     
       55. The process  claim 54 , wherein said process further comprises passing said feed stream over at least one adsorbent layer upstream of said CO adsorbent for the adsorption of one or more of H 2 O and CO 2  to produce a H 2 O and or CO 2  depleted feed stream. 
     
     
       56. The process of  claim 54 , wherein said process further comprises, passing said feed stream over a catalyst layer that is downstream of said CO adsorbent layer for the catalytic conversion of H 2  to H 2 O layer and one or more additional adsorbents for the adsorption of one or more of H 2 O, CO 2 , N 2 O and hydrocarbons, wherein said additional adsorbents are downstream of said catalyst layer to produce a feed stream that is depleted in CO, H 2  and one or more of H 2 O, CO 2 , N 2 O and hydrocarbons. 
     
     
       57. The process of  claim 54 , wherein said CO adsorbent is AgX. 
     
     
       58. The process of  claim 54 , wherein the depleted feed stream is passed to a cryogenic distillation column for the separation of air.

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